CN110180008A - It is a kind of with release Xiang Gong can cyclodextrin metal organic frame inclusion compound and preparation method thereof - Google Patents
It is a kind of with release Xiang Gong can cyclodextrin metal organic frame inclusion compound and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
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- A—HUMAN NECESSITIES
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- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
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Abstract
The invention belongs to fragrance loads and sustained release field, it specifically discloses a kind of with the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, it is made after being included by cyclodextrin metal organic frame and ester perfume, the cyclodextrin metal organic frame is 200~300mg/g to the amount of containing of ester perfume；For the crystal particle diameter of the cyclodextrin metal organic frame having a size of 300~500nm, the pore-size distribution of micropore is 0.5~2nm, and specific surface area is 900~980m2g‑1.Inclusion compound of the invention significantly improves the amount of containing of ester perfume, and achievees the effect that sustained release, also has application prospect in health care and cosmetic field.The invention also discloses the preparation methods of the cyclodextrin metal organic frame inclusion compound, and preparation process is simple, is suitable for industrialized production.
Description
Technical field
The invention belongs to fragrance loads and sustained release field, and in particular to a kind of organic with the cyclodextrin metal for releasing Xiang Gong energy
Frame inclusion compound and preparation method thereof.
Technical background
With the development of society, people's quality of the life is continuously improved, so that the demand to fragrance and fragrance is also constantly increasing
Add.Perfume molecules are mainly made of small molecule, are had very strong volatility, are often added in various products, bring and make us
Pleasant smell, but all there is poorly water-soluble, oxidizable easy polymerization and unstable etc. by such environmental effects in most of fragrance
Defect also limits it and effectively uses.
Spice slow-releasing system is a certain special nature by carrying out certain processing or dependence auxiliary material to fragrance, is made
Its object discharges slowly or controllably in release medium.The material of different types of carried perfume, it is a variety of to have biology
The high molecular material of degradability and biocompatibility is used for carried perfume, mixes high molecular material as substrate and fragrance
It closes, then removes solvent medium using means such as freeze-drying, spray drying, obtain perfume molecules and be uniformly distributed in substrate web
Mixed system in structure.
Biological macromolecule material such as chitosan, cyclodextrin etc. is also also constantly used to perfume (or spice) because its is cheap, green non-poisonous
Material contains.As the Patent Application Publication of Publication No. CN108245684A discloses a kind of menthol hydroxypropyl cyclodextrin inclusion
The preparation method of object, gained inclusion compound reach completely water-soluble, overcome that menthol stability is poor, and the big defect of irritation expands
Its application in health care and cosmetic field.Procter&Gamble has also applied for the relevant patent of multinomial cyclodextrin,
Technology is contained to a variety of fragrance as the Patent Application Publication of Publication No. US20040127463M discloses cyclodextrin, the inclusion
Proper amount of surfactant is added in object and antibacterial material, gained inclusion compound are stable in the presence of in aqueous solution, reaches purification air
Effect.
Based on molecular encapsulation technology, cyclodextrin and its derivative have been obtained extensive in terms of the containing with sustained release of fragrance
Using, it will usually it is water-soluble that certain chemical modification raising is carried out to cyclodextrin, but chemically reacts complicated and destroys its biology spy
Property.
Porous material has biggish specific surface area, has inertia, such as zeolite, molecular sieve and gold in target environment
Belong to frame material and is also used as containing for fragrance extensively.As the Patent Application Publication of Publication No. CN 108929777A discloses
A kind of MOF material load control release type perfume, organic ligand contains hydroxyl in MOF material organic ligand, make itself and porous substrate it
Between realize insertion, attachment, become good spice slow-releasing particle.
But using porous material for example zeolite carry out fragrance absorption when, fragrance adsorb only on zeolite surface and blame into
Enter in its hole, absorption stability is poor, easily leads to phenomenon of burst release.And the fragrance that can be applied to being recently proposed contains and sustained release field
MOF material, such as Uio-66, MIL-101, water solubility is poor, spray formulation can not be made into, organic matter present in ligand
Toxicity is unfavorable for washing in the fields such as shield, cosmetics applied to health care, individual.Therefore, finding has good biocompatibility,
The stable fragrance adsorbent material of environmental protection becomes the emphasis for concern.
Summary of the invention
The object of the present invention is to provide it is a kind of with release Xiang Gong can cyclodextrin metal organic frame inclusion compound and its
Preparation method passes through cyclodextrin metal organic framework (cyclodextrin metal-organic framework, CD-MOF)
Specific fragrance is loaded, unstable, high volatility specific fragrance is made to realize obvious slow release effect.
Technical scheme is as follows:
It is a kind of with release Xiang Gong can cyclodextrin metal organic frame inclusion compound, by cyclodextrin metal organic frame (CD-
MOF be made after) being included with ester perfume, the cyclodextrin metal organic frame to the amount of containing of ester perfume be 200~
300mg/g；
The crystal particle diameter of the cyclodextrin metal organic frame is having a size of 300~500nm, the pore-size distribution of micropore
0.5~2nm, specific surface area are 900~980m2g-1。
The host molecule of inclusion compound of the present invention is the good cyclodextrin metal organic frame porous material of biocompatibility, should
Material has biggish specific surface area, and uniform nano-scale, good thermal stability can will be unstable, high volatility
Liquid ester perfume is stored in solid porous material, and high to the ester perfume amount of containing and stable, slow release effect is obvious, half-life period
At 15 days or more, which is expected to release fragrant material as good solid.
The preparation method of the cyclodextrin metal organic frame, includes the following steps:
(1) in closed environment, methanol is diffused by steam in the mixed solution of cyclodextrin and potassium hydroxide, centrifugation
Filter to take filtrate；
(2) methanol and surfactant are added in filtrate, stands, centrifugation, precipitating obtains cyclodextrin metal after post treatment
Organic frame.
The preparation process of the cyclodextrin metal organic frame can undergo two times of crystallization, and crystallization is due to first for the first time
Alcohol is diffused by steam in the mixed solution of cyclodextrin and potassium hydroxide, and white crystal can constantly be analysed from mixed solution
Out；Second of crystallization is methanol and surfactant to be added in filtrate to regulate and control crystalline size, has obtained receiving for specific dimensions
The CD-MOF crystal of meter level.
Preferably, in step (1), the cyclodextrin is gamma-cyclodextrin.This is because gamma-cyclodextrin safety edible is used,
And the specific surface area of gamma-cyclodextrin metal organic frame obtained is relatively high, crystalline form is preferable, and stability is good, contains to fragrance
Amount is high, and slow release effect is obvious.
Gamma-cyclodextrin metal organic framework obtained (γ-cyclodextrin metal-organic framework,
γ-CD-MOF) material is by K+It is self-assembly of with γ-CD by coordinate bond, synthesis process is naturally had safely using material
Edibility feature, avoid using phthalic acid and trimesic acid etc. have genotoxic potential organic ligand and chromium, cobalt,
The heavy metal ion such as nickel.
Monocrystalline XRD shows that basic unit can be expressed as [(γ-CD)6(KOH)2]n, six cyclodextrin moleculars account for respectively
According to six faces of cube, the cavity of a 1.7nm is formed, chelating is coordinated in two ways for cyclodextrin and K ion, generates three-dimensional hand over
It is coupled structure, and then forms body-centered accumulation, forms more small apertures.Different from " internal drainage, external hydrophilicity " rotary table knot of γ-CD
Structure, the macropore for the 1.7nm that γ-CD-MOF is formed have hydrophily, and biggish internal cavities load more amphiphilic esters for it
Class perfume molecules provide space.
In step (1), the temperature in the steam diffusion process is 30~50 DEG C, and diffusion time is 5~7h.Step (2)
In, the surfactant is cetyl trimethylammonium bromide (CTAB), and the time of the standing is 10~14h.
During above-mentioned preparation CD-MOF, organic ligand cyclodextrin (CD) is coordinated in two ways with potassium ion, is formed
Body centred cubic packing, cyclodextrin molecular occupy six faces of cube.Again by methanol is diffused under given conditions with
It controls the evaporation rate of methanol and adds specific surfactant, to obtain the nanoscale CD-MOF crystal of specific dimensions.
The ester perfume is ethyl propionate or ethyl 2-methylbutyrate.
Its packet load ranges is determined using nuclear-magnetism method, cyclodextrin metal organic frame is 220 to the amount of containing of ethyl propionate
~250mg/g, cyclodextrin metal organic frame are 270~290mg/g to the amount of containing of ethyl 2-methylbutyrate.
Above-mentioned fragrance-cyclodextrin metal organic frame inclusion compound preparation method, comprising: by the cyclodextrin gold after activation
Belong to organic frame to immerse in ester perfume solution, shake 12 under the conditions of 20~30 DEG C~for 24 hours, using washing, be dried to obtain
The cyclodextrin metal organic frame inclusion compound.
Compared with the prior art, the present invention has the following beneficial effects:
(1) even size distribution of CD-MOF of the invention, control in 300~500nm, have good nanostructure and
Thermal stability makes it that can preferably realize insertion and attachment between porous substrate, becomes a kind of good spice slow-releasing particle；
(2) synthesis material of CD-MOF of the invention comes from edible gamma-cyclodextrin, and potassium ion is also the required member of body
Element has good biocompatibility, therefore what the material can be safe is applied to health care, food, cosmetics or individual
Fields, the application ranges such as nursing are extremely extensive；
(3) inclusion compound of the invention improves the amount of containing of ester perfume, and significantly improves the sustained release effect of ester perfume
Fruit；And the inclusion compound is disclosed to the maximum amount of containing of specific fragrance, perfume molecules can be made well into material hole, avoided
Excessive fragrance residual leads to phenomenon of burst release on the surface of the material.
(4) inclusion compound of the invention is solid powder state, relative to the inclusion compounds existence form such as lotion, suspension,
Pulverulence is with good stability, being capable of long-term preservation.
(5) present invention contains fragrance using infusion process, and preparation process is simple, is suitable for industrialized production, after containing
Excessive fragrance can be with recycling and reusing, and the inclusion compound can also be recycled and be contained again after fragrance discharges, and be realized
It recycles, there is stronger economic value and environment protection significance.
Detailed description of the invention
Nitrogen adsorption-the desorption isotherm and graph of pore diameter distribution of γ-CD-MOF made from Fig. 1 embodiment 1；
Fig. 2 is the infrared spectrogram of inclusion compound made from embodiment 1 and comparative example 3, wherein A is γ-CD/EP, and B is γ-
CD-MOF/EP；
Fig. 3 is the nuclear magnetic spectrogram of γ-CD-MOF/EP inclusion compound made from embodiment 1；
Fig. 4 is the fragrance releasing curve diagram of inclusion compound made from Examples 1 to 2 and comparative example 3~4.
Specific embodiment
Embodiment 1: preparation γ-CD-MOF/EP inclusion compound
(1) it prepares γ-CD-MOF: weighing γ-CD (810mg, 0.625mmol) and KOH (280mg, 5mmol), be dissolved in
In the distilled water of 25mL, by mixed liquor by 0.45 μm of PTFE membrane filtration, it is placed in glass beaker.Glass is placed in and is filled
In the closed system of full methanol, 6h is stood at 40 DEG C, precipitating is cast out in centrifugation, be added in mother liquor isometric methanol solution with
CTAB (200mg), stands overnight, mixed liquor is centrifuged, and washs precipitating 3 times with isopropanol, removes excess CTAB.By white crystal
It is impregnated 3 days in dichloromethane solution, replaces a solvent daily, white crystal is finally put into 38 DEG C of vacuum drying oven dryings and is removed
Remove the solvent in duct.
(2) γ-CD-MOF/EP inclusion compound is prepared using infusion process: takes the γ-CD-MOF of 20mg in 10mL centrifuge tube,
Add the ethyl propionate solution of 2mL.Centrifuge tube is placed in concussion instrument and shakes 12h, perfume molecules are carried on the hole γ-CD-MOF
In road, after being washed with n-hexane, taken out after being placed in 40 DEG C of baking ovens dry 2h, as γ-CD-MOF/EP inclusion compound.
γ-CD-MOF (10~15mg) after taking step (1) activation obtained, placing it in 100 DEG C, to vacuumize removal of impurities 6 small
When, its specific surface area and pore-size distribution are tested with nitrogen physisorption instrument, specific surface area and graph of pore diameter distribution such as Fig. 1 institute measured
Show.
As shown in Figure 1, the adsorption isothermal curve of γ-CD-MOF obtained belongs to II type thermoisopleth, due to adsorbate and table
Face is there are stronger interaction, (the P/P under lower relative pressure0< 0.05) adsorbance rises rapidly.With relative pressure
Continue growing, multilayer absorption gradually form, adsorbance is gradually stable.Measuring its specific surface area according to BET equation is 951m2g-1, by its aperture of HK equation calculation, pore size is distributed at 0.7nm, 1.0nm, 1.2nm, 1.7nm, it was demonstrated that material has micro-
Pore structure (< 2nm).
Embodiment 2: preparation γ-CD-MOF/EMB inclusion compound
It is prepared using the method for embodiment 1, in addition to replacing with ethyl 2-methylbutyrate (EMB) fragrance ethyl propionate, is made
Obtain γ-CD-MOF/EMB inclusion compound.
Comparative example 1: preparation γ-CD-MOF/LM inclusion compound
It is prepared using the method for embodiment 1, in addition to fragrance ethyl propionate is replaced with nonpolar terpene fragrance limonene
(LM), γ-CD-MOF/ limonene inclusion complex is made.
Comparative example 2: preparation γ-CD-MOF/My inclusion compound
It is prepared using the method for embodiment 1, in addition to fragrance ethyl propionate is replaced with nonpolar terpene fragrance laurene
(My), γ-CD-MOF/ laurene inclusion compound is made.
Comparative example 3: preparation γ-CD/EP inclusion compound
Prepared using desivac: the γ-CD for weighing 20mg is dissolved in containing in the centrifuge tube in 5mL distilled water, is added
The ethyl propionate of 500uL, centrifuge tube is placed in concussion instrument, is shaken 12h, is centrifuged off upper layer excess ethyl propionate.By solution
White powder solid, as γ-CD/EP inclusion compound are obtained after freeze-drying.
Comparative example 4: preparation γ-CD/EMB inclusion compound
It is prepared using the method for comparative example 3, in addition to replacing with ethyl 2-methylbutyrate (EMB) fragrance ethyl propionate, is made
Obtain γ-CD/EMB inclusion compound.
Comparative example 5: preparation γ-CD/LM inclusion compound
It is prepared using the method for comparative example 3, in addition to fragrance ethyl propionate is replaced with nonpolar terpene fragrance limonene
(LM), γ-CD/LM inclusion compound is made.
Comparative example 6: preparation γ-CD/My inclusion compound
It is prepared using the method for comparative example 3, in addition to fragrance ethyl propionate is replaced with nonpolar terpene fragrance laurene
(My), γ-CD/My inclusion compound is made.
Performance and structure determination:
(1) interaction of fragrance and carrier is probed into using FTIR spectrum method:
Inclusion compound made from embodiment 1 and comparative example 3 is measured into infrared spectroscopy using pellet technique respectively, uses liquid film
Method measures pure fragrance infrared spectroscopy, and the infrared spectrogram measured is as shown in Figure 2.
As shown in Figure 2, the carbonyl characteristic peak of pure fragrance ethyl propionate is in 1740cm-1Place, γ-CD/ ethyl propionate inclusion compound
In 1717cm-1Place observes carbonyl characteristic peak, and γ-CD-MOF/ ethyl propionate inclusion compound is in 1721cm-1Observe carbonyl spy in place
Peak is levied, obvious Red Shift Phenomena (23cm all occurs respectively in inclusion compound-1,19cm-1), it was demonstrated that between esters and carrier there are hydrogen bonds
Interaction.
(2) γ-CD/ fragrance and γ-CD-MOF/ spices bag loading contains ability:
γ-CD-MOF/EP the inclusion compound for taking 5~10mg embodiment 1 to prepare is dissolved in deuterated water, is monitored and is wrapped using nuclear-magnetism
Carrying capacity.From the figure 3, it may be seen that γ-CD in chemical shift 5.0ppm (- OCH-) integrated value is set as 8 in inclusion compound, 1 γ-CD points are represented
Son；Ethyl propionate is in chemical shift 1.0ppm (- CH in inclusion compound3) integrated value be 9.05, represent 1.04 ethyl propionate molecules.
Ratiometric result is shown: γ-CD-MOF/ ethyl propionate is contained than for 1:3.02, it follows that γ-CD-MOF is compared to-CD pairs of γ
The amount of containing of fragrance obviously increases.
(3) release conditions of γ-CD/ fragrance and γ-CD-MOF/ spices bag loading:
Using solid phase microextraction-gas-chromatography combination means to inclusion compound made from Examples 1 to 2 and comparative example 3~4
Release conditions are monitored, and take the γ-CD/EP inclusion compound of 10mg in the ml headspace bottle of 20mL, are fixed 1~2 day and are taken a monitoring, note
Record release conditions.It takes the γ-CD-MOF/EP inclusion compound of 10mg in the ml headspace bottle of 20mL, fixes 1~2 day and take a monitoring, record
The fragrance releasing curve diagram of release conditions, drafting is as shown in Figure 4.
As shown in Figure 4, inclusion compound fragrance rate of release produced by the present invention obviously slows down, half-life period at 10 days or more,
Embodiment has reached good slow release effect relative to pure fragrance and comparative example.
The gas chromatograph parameters of above-mentioned monitoring process are as follows:
Agilent 19091J-413 type chromatographic column (30m*320um*0.25um)；
250 DEG C of preceding injector temperature；
250 DEG C of flame detector temperature；
Column temperature program setting are as follows: 50 DEG C of initial temperature, rise to 230 DEG C with the heating rate of 10 DEG C/min, keep
20min。
Inclusion compound made from Examples 1 to 2 and comparative example 1~6 is observed respectively to the absorption situation of fragrance, adsorbance test
Condition: it takes 5~10mg to contain the MOF material of ester perfume, is dissolved in deuterated water, 400MHz Nuclear Magnetic Resonance is in room temperature condition
Lower test analyzes its amount of containing using nuclear magnetic spectrogram is obtained.Terpene spices bag carrying capacity test condition is same as above, and 10~15mg is taken to contain
The MOF material of terpene fragrance, deuterated reagent DMSO-d6.
The adsorbance respectively obtained is as shown in table 1 below.
Table 1
| Group | Carrier | Organic perfume | Adsorbance (mg/g) |
| Embodiment 1 | γ-CD-MOF | Ethyl propionate | 218 |
| Embodiment 2 | γ-CD-MOF | Ethyl 2-methylbutyrate | 285 |
| Comparative example 1 | γ-CD-MOF | Limonene | 99 |
| Comparative example 2 | γ-CD-MOF | Laurene | 105 |
| Comparative example 3 | γ-CD | Ethyl propionate | 72 |
| Comparative example 4 | γ-CD | Ethyl 2-methylbutyrate | 93 |
| Comparative example 5 | γ-CD | Limonene | 94 |
| Comparative example 6 | γ-CD | Laurene | 93 |
As shown in Table 1, γ-CD-MOF obviously increases the adsorbance of ester perfume relative to γ-CD, and γ-CD-MOF
There is no significant change relative to γ-CD to the adsorbance of terpene fragrance.This is compared based on the unique pore structure of γ-CD-MOF
The macropore of the 1.7nm newly formed in the single hydrophobicity inner hole of γ-CD, γ-CD-MOF has hydrophily, with amphiphilic ester
Class fragrance active force is stronger, and weaker with nonpolar terpene fragrance active force, so causing the difference for the amount of containing.Therefore,
Cyclodextrin metal-organic framework material in the present invention is more suitable for containing amphipathic ester perfume.
Claims (10)
1. a kind of with the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that organic by cyclodextrin metal
Frame and ester perfume are made after being included, the cyclodextrin metal organic frame to the amount of containing of ester perfume be 200~
300mg/g；
The crystal particle diameter of the cyclodextrin metal organic frame is 0.5 having a size of 300~500nm, the pore-size distribution of micropore
~2nm, specific surface area are 900~980m2g-1。
2. according to claim 1 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that institute
The preparation method for the cyclodextrin metal organic frame stated, includes the following steps:
(1) in closed environment, methanol is diffused by steam in the mixed solution of cyclodextrin and potassium hydroxide, centrifugal filtration
Take filtrate；
(2) methanol and surfactant are added in filtrate, stands, centrifugation, it is organic that precipitating obtains cyclodextrin metal after post treatment
Frame.
3. according to claim 2 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that step
Suddenly in (1), the cyclodextrin is gamma-cyclodextrin.
4. according to claim 2 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that step
Suddenly in (1), it is 5~7h that the temperature in the steam diffusion process, which is 30~50 DEG C of diffusion times,.
5. according to claim 2 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that step
Suddenly in (2), the surfactant is cetyl trimethylammonium bromide.
6. according to claim 2 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that step
Suddenly in (2), the time of the standing is 10~14h.
7. according to claim 1 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that institute
The ester perfume stated is ethyl propionate or ethyl 2-methylbutyrate.
8. according to claim 7 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that institute
The cyclodextrin metal organic frame stated is 220~250mg/g to the amount of containing of ethyl propionate.
9. according to claim 7 have the cyclodextrin metal organic frame inclusion compound for releasing Xiang Gong energy, which is characterized in that institute
The cyclodextrin metal organic frame stated is 270~290mg/g to the amount of containing of ethyl 2-methylbutyrate.
10. fragrance according to claim 1-cyclodextrin metal organic frame inclusion compound preparation method, comprising: will activate
Rear cyclodextrin metal organic frame immerses in ester perfume solution, shakes 12 under the conditions of 20~30 DEG C~for 24 hours, using washing
It washs, be dried to obtain the cyclodextrin metal organic frame inclusion compound.
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| CN110922329A (en) * | 2019-11-29 | 2020-03-27 | 浙江大学 | Metal organic framework material prepared based on potassium sorbate emulsion and preparation method thereof |
| CN111440325A (en) * | 2020-02-25 | 2020-07-24 | 浙江大学 | Cyclodextrin metal organic framework material and preparation thereof |
| CN112300425A (en) * | 2020-11-17 | 2021-02-02 | 上海海洋大学 | Gelatin/fiber composite antibacterial film and preparation method and application thereof |
| CN113786396A (en) * | 2021-08-20 | 2021-12-14 | 华南理工大学 | Thymol-loaded cyclodextrin complex and preparation method thereof |
| CN115109322A (en) * | 2022-06-20 | 2022-09-27 | 宁波大学 | Preparation method and application of gamma-cyclodextrin metal-organic framework film loaded with terpinene-4-alcohol |
| CN115251058A (en) * | 2022-09-02 | 2022-11-01 | 重庆喜旋生物科技有限公司 | DEET slow-release aromatherapy wax, preparation method and application |
| CN115413652A (en) * | 2022-08-31 | 2022-12-02 | 中国农业科学院植物保护研究所 | Gamma-cyclodextrin-metal organic framework material loaded biopesticide sustained release agent and preparation method thereof |
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